Phosphole and diphosphole ligands for catalysis

ABSTRACT

Novel reactions used to prepare phosphole and bisphosphole compounds are detailed. Novel phosphole compounds and metal coordination compounds of phosphole and bisphosphole compounds are also provided. These metal coordination compounds are useful as catalysts for the polymerization or olefins with carbon monoxide and for the polymerization of acrylic monomers.

This application is a Divisional Application of Ser. No. 10/411,997filed Apr. 11, 2003 now U.S. Pat. No. 6,800,719; which is a divisionalof Ser. No. 10/044,425 filed Nov. 13, 2001, now U.S. Pat. No. 6,579,999,which is a divisional of Ser. No. 09/650,608 filed Aug. 30, 2000 nowU.S. Pat. No. 6,350,903; which is a divisional of Ser. No. 09/415,388filed Oct. 8, 1999 now U.S. Pat. No. 6,137,012; which is anon-provisional of Ser. No. 60/104,112 filed Oct. 13, 1998, which is nowpending.

FIELD OF INVENTION

The invention relates to new phosphole and diphosphole based ligandsuseful as polymerization catalysts.

BACKGROUND

The phosphole ring system is described by structure A. This structure isdistinct from the class of compounds B which contain benzo rings fusedto the phosphole core.

Class I has a much different electronic structure and therefore has muchdifferent chemistry than compounds of class II. In class I, the P atomis part of the delocalized, partially aromatic ring system. In class II,the aromaticity is confined to the benzo rings, with no delocalizationaround the P atom. Class I will participate in Diels-Alder chemistry(especially when complexed to a metal) (Bhaduri et al., Organometallics1992, 11, pp. 4069-4076), whereas compounds of class II will not (Quin,Compr. Heterocycl. Chem. II Bird, Clive W (Ed), 1996, Vol. 2, pp.757-856).

Very few compounds have been reported that contain two phosphole ringsconnected via a bridge (A) between the phosphorus atoms (structure C)(A=bridging hydrocarbon, hydrocarbon/heteroatom(s), or organometallicgroup).

One explanation for the paucity of compounds of type C-G is the lack ofsynthetic procedures broad enough in scope to prepare the phosphole ringsystem.

Examples reported in the literature include the compounds 1 (Braye etal., Tetrahedron 1971, pp. 5523-37), 2 (A=—CH₂—, —CH₂CH₂—, and—CH═CH—CH═CH—) (Charrier et al., Organometallics 1987, 6 pp. 586 91),and 3 (Gradoz et al., J. Chem. Soc. Dalton Trans. 1992, pp. 3047-3051).

Compounds containing a single phosphole ring (I) were made using theFagan-Nugent heterocycle synthesis (Fagan et al., J. Am. Chem. Soc.1994, 116, pp. 1880-1889; Fagan et al., J. Am. Chem. Soc. 1988, 110, pp.2310-2312). This synthesis involves preparing the zirconium reagents bycoupling of acetylenes followed by transfer of the metallacycle fromzirconium to phosphorus. In all cases, the substituent on the phosphoruswas an aromatic group such as phenyl.

These types of compounds (containing a single phosphole ring) have foundlimited utility as ligands for transition metals for use in catalysis,and have been shown to have different chemistries than their phosphineanalogs (Neibecker et al., New J. Chem. 1991, pp. 279-81; Neibecker etal., J. Mol. Catal. 1989, 57 pp. 153-163; Neibecker et al., J. Mol.Catal. 1989, 219-227; Vac et al., Inorg. Chem. 1989 28, pp. 3831-3836;Hjortkjaer et al., J. Mol. Catal. 1989 50, 203-210).

Transition metal complexes have been made using structures of class VII,shown below, where the rings are linked at the position alpha tophosphorus. Attempts to use these ligands to make Pd acetonitrilecomplexes analogous to those in the instant invention failed (Guoygou etal., Organometallics 1997, 16, 1008-1015).

Copolymers of carbon monoxide and olefins, such as ethylene, can be madeby free radical initiated copolymerization (Brubaker, J. Am. Chem. Soc.,1952, 74, 1509) or gamma-ray induced copolymerization (Steinberg, Polym.Eng. Sci., 1977, 17, 335). The copolymers produced were randomcopolymers and their melting points were low. In 1951, Reppe discovereda nickel-catalyzed ethylene carbon monoxide copolymerization system thatgave alternating copolymers (U.S. Pat. No. 2,577,208 (1951)). However,the molecular weights of these polymers were also low.

In 1984, U.S. Pat. Nos. 4,818,810 and 4,835,250 disclosed the productionof alternating olefin carbon monoxide copolymers based on Pd(II), Ni(II)and Co(II) complexes bearing bidentate ligands of the formulaR₁R₂E-A-E-R₃R₄, wherein R₁, R₂, R₃, R₄, and A are organic groups and Eis phosphorus, arsenic, or antimony. When E is phosphorus and R₁₋₄ arearyl groups, the corresponding diphosphine palladium complexes areactive in copolymerizing ethylene and carbon monoxide to producecopolymers of molecular weight up to 30,000 (MW_(n)) (Drent et al.,Chem. Rev., 1996, 96, 663). No compounds were claimed or disclosed inwhich R₁ and R₂, and R₃ and R₄ together formed a ring. Applicants haverecently found that the diphosphole coordinated palladium catalystscatalyze olefin/carbon monoxide (CO) copolymerization. When the P atomis part of a ring system, the electronic environment and thereforeexpected chemistries are different than simple, non-ring phosphinedisclosed in the patents described above.

Radical polymerization is an important commercial process for making avariety of polymers of vinyl monomers, such as acrylics and styrenics.While this process makes large amounts of polymers, the difficulty inaccurately controlling the polymer structures (such as molecular weight,molecular weight distribution, and architecture, etc.) has significantlylimited its further applications.

Living polymerization usually offers much better control on polymerstructures and architectures. While living polymerization systems foranionic, cationic, and group transfer mechanisms were developed someyears ago, a true living radical polymerization system is still anelusive goal (because of the high reactivity of free radicals) and onlyvery recently has pseudo-living radical polymerization been achieved.One pseudo-living radical polymerization method is “atom transferradical polymerization” (ATRP). In this process a transition metalcompound, usually in a lower valent state, is contacted with a compoundwhich is capable of transferring an atom to the metal complex, therebyoxidizing the metal to a higher valent state and forming a radical whichcan initiate polymerization. However, the atom that was transferred tothe metal complex may be reversibly transferred back to the growingpolymer chain at any time. In this way, the propagation step isregulated by this reversible atom transfer equilibrium and statisticallyall polymer chains grow at the same rate. The results a pseudo-livingradical polymerization in which the molecular weight may be closelycontrolled and the molecular weight distribution is narrow.

Such ATRPs are described in many publications (Kato et al.,Macromolecules 1995, 28, 1721; Wang et al., Macromolecules 1995, 28,7572; Wang et al., Macromolecules 1995, 28, 7901; Granel et al.,Macromolecules 1996, 29, 8576; Matyjaszewski et al., PCT WO 96/30421).The transition metal complexes used include complexes of Cu(I), Ru(II),Ni(II), Fe(II), and Rh(II). The complexes are formed by coordinating themetal ions with certain ligands such as nitrogen or phosphine containingligands. For Ru(II) and Fe(II), mono-phosphine P(C₆H₅)₃ was used as theligand. However, for Cu(I), all the ligands used are nitrogen-based suchas bipyridine or substituted bipyridine. No phosphine-based ligand hasbeen shown to be an effective ligand for Cu(I) in ATRP.

It has been found that novel types of ligands containing phosphole andother P ring systems can chelate Cu(I) to form active catalysts forATRP.

SUMMARY OF THE INVENTION

An object of this invention is to provide a process for the preparationof compounds of formulae I and II

by reacting a compound of formula X₂P-A-PX₂ (III) with a compound offormula IV;

wherein R₁, R₂, R₃ and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₂ andR₃ together can optionally form a ring; Cp is cyclopentadienyl; X isselected from the group consisting of Cl, Br, and I; A is a divalentgroup consisting of optionally-substituted chains of from 1 to 12linear, branched, or cyclic carbons, optionally containing one or moreheteroatoms or organometallic groups in the chain, and —N(R₇)—N(R₈)—;and R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

Preferably A is selected from the group consisting of a carbon chain of1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, andsubstituted hydrocarbyl. More preferably R₁, R₂, R₃ and R₄ are alkylgroups.

The invention also provides for a compound of the formula

wherein R₁, R₂, R₃ and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; Cp iscyclopentadienyl (η⁵—C₅H₅); A is a divalent group consisting ofoptionally-substituted chains of from 1 to 12 linear, branched, orcyclic carbons, optionally containing one or more heteroatoms ororganometallic groups in the chain, and —N(R₇)—N(R₈)—; and R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.

Preferably A is selected from the group consisting of a carbon chain of1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, andsubstituted hydrocarbyl. More preferably R₁, R₂, R₃ and R₄ are alkylgroups and R₅ and R₆ are selected from the group consisting of alkylgroups and Cl.

A further object of the invention is a coordination compound comprisingone or more transition metals complexed to one or more of the followingcompounds as ligands:

wherein R₁, R₂, R₃ and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.

Preferably the transition metal is Pd and A is selected from the groupconsisting of a carbon chain of 1-3 carbons and —N(R₇)—N(R₈)—, whereinR₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl. More preferably R₁,R₂, R₃, and R₄ are alkyl groups and R₅ and R₆ are selected from thegroup consisting of alkyl groups and Cl.

The invention also provides a process for the preparation of apolyketone by contacting a mixture of carbon monoxide with one or morealkenes under polymerization conditions with a catalyst comprising atransition metal complexed with one or more ligands of the formulae IIAor VA

wherein the rings are optionally-substituted and are optionally membersof a larger bicyclic or tricyclic ring system; each P atom is bonded toonly three other atoms in the ligand; the two atoms in the ring adjacentto the P atom are C atoms; R₅ and R₆ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, Cl,Br, I, N, O, and S; R₅ and R₆ together can optionally form a ring; A isa divalent group consisting of optionally-substituted chains of from 1to 12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.

Preferably the transition metal is Pd and the ligand is of the formulaeV or II

wherein R, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. Morepreferably A is selected from the group consisting of a carbon chain of1-3 carbons and —N(R₇)—N(R₈)—, R₇ and R₈ are independently selected fromthe group consisting of hydrogen, hydrocarbyl, and substitutedhydrocarbyl R₁, R₂, R₃, and R₄ are alkyl groups, R₅ and R₆ are selectedfrom the group consisting of alkyl groups and Cl, and the alkene isethylene.

Another object of the invention is a process for the polymerization ofan acrylic monomer by contacting at least one acrylic monomer underpolymerization conditions with a catalyst comprising Cu(I) complexedwith one or more ligands of the formulae IIA or VA

wherein the rings are optionally-substituted and are optionally membersof a larger bicyclic or tricyclic ring system; each P atom is bonded toonly three other atoms in the ligand; the two atoms in the ring adjacentto the P atom are C atoms; R₅ and R₆ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, Cl,Br, I, N, O, and S; R₅ and R₆ together can optionally form a ring; A isa divalent group of optionally-substituted chains of from 1 to 12linear, branched, or cyclic carbons, optionally containing one or moreheteroatoms or organometallic groups in the chain, and —N(R₇)—N(R₈)—;and R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

Preferably the ligand is of the formulae V or II

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. Morepreferably A is selected from the group consisting of a carbon chain of1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, andsubstituted hydrocarbyl, R₁, R₂, R₃, and R₄ re alkyl groups, R₅ and R₆are selected from the group consisting of alkyl groups and Cl, and theacrylic monomer is methylmethacrylate.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides novel reactions used to prepare phosphole andbisphosphole compounds. Novel phosphole compounds and metal coordinationcompounds of phosphole and bisphosphole compounds are also provided.These metal coordination compounds are useful as polymerizationcatalysts.

The present invention provides processes for the preparation ofbisphosphole compounds of formulae I and II

by reacting a compound of formula IV with a compound of formulaX₂P-A-PX₂ (III);

wherein:

R₁, R₂, R₃, and R₄ are independently selected from the group consistingof hydrogen, hydrocarbyl, and substituted hydrocarbyl;

R₂ and R₃ together can optionally form a ring;

Cp is cyclopentadienyl (η⁵-C₅H₅);

X is selected from the group consisting of Cl, Br, and I;

A is a divalent group consisting of optionally-substituted chains offrom 1 to 12 linear, branched, or cyclic carbons, optionally containingone or more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and

R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

By hydrocarbyl is meant a straight chain, branched or cyclic arrangementof carbon atoms connected by single, double, or triple carbon to carbonbonds and/or by ether linkages, and substituted accordingly withhydrogen atoms. Such hydrocarbyl groups may be aliphatic and/oraromatic. Examples of hydrocarbyl groups include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, t-butyl, cyclopropyl, cyclobutyl,cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, benzyl,phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, vinyl, allyl, butenyl,cyclohexenyl, cyclooctenyl, cyclooctadienyl, and butynyl. Examples ofsubstituted hydrocarbyl groups include toluyl, chlorobenzyl,fluoroethyl, p-CH₃—S—C₆H₅, 2-methoxy-propyl, and (CH₃)₃SiCH₂.

“Coordination compound” refers to a compound formed by the union of ametal ion (usually a transition metal) with a non-metallic ion ormolecule called a ligand or complexing agent.

Preferred compounds of formulae II and I include those where A isselected from the group consisting of —N(R₇)—N(R₈)— and carbon chains of1-3 carbons. Also preferred are compounds of formulae III and IV whereR₁, R₂, R₃, and R₄ are alkyl groups. Most preferred are1,2-bis(2,3,4,5-tetramethyl-phospholyl)ethane;1,2-bis(2,3,4,5-tetraethylphospholyl)ethane;1,1-bis(2,3,4,5-tetramethylphospholyl)methane;1,1-bis(2,3,4,5-tetraethylphospholyl)methane;1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine;1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane; and1-(2,3,4,5-tetramethyl-phospholyl)-2-dichlorophosphinoethane-1,2-dimethylhydrazine.

The process can be run in a wide variety of solvents. Preferred solventsare CH₂Cl₂ and THF (tetrahydrofuran). Low temperatures, below from about−100° C. to room temperature, are typically used.

The zirconium reagents (IV) are first prepared by reacting Cp₂ZrCl₂(Cp=η⁵-C₅H₅, cyclopentadienyl) with n-BuLi at about −78° C. followed bywarming in the presence of an alkyne, alkynes, or dialkyne. Themetallacycles can be isolated, or used in situ. When these are reactedwith one-half of a molar equivalent of a diphosphorus compoundX₂P-A-PX₂, compounds of formula II result (Scheme 1).

If zirconium metallacycles of type IV are reacted with at least oneequivalent of the phosphorus reagents X₂P-A-PX₂, then compounds offormula I can be prepared (Scheme 2).

Dialkynes provide zirconium metallacycles of formula IVA which can bereacted with X₂P-A-PX₂ to form compounds of formula II wherein R₂ and R₃together form a ring as illustrated in Scheme 3.

where Z is any linking group with proper orientation or is flexibleenough to allow the reaction to proceed. Examples of suitable linkinggroups include hydrocarbyl, substituted hydrocarbyl, and organometalliccompounds. Preferred is —(CH₂)_(x)—, where X is 1-10.

The above reactions should be performed under a N₂ atmosphere usinganhydrous solvents.

Similarly, the products from reaction of zirconium metallacycles IVAallows the corresponding compounds of formula I wherein R₂ and R₃together form a ring to be prepared (Scheme 4).

The present invention also provides for novel phosphole compositions ofthe formula V

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;

R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S;

R₂ and R₃ together and R₅ and R₆ together can optionally form a ring;

A is a divalent group consisting of optionally-substituted chains offrom 1 to 12 linear, branched, or cyclic carbons, optionally containingone or more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and

R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

Preferred compounds of formulae V include those where A is selected fromthe group consisting of —N(R₇)—N(R₈)— and carbon chains of 1-3 carbons.Also preferred are compounds of formulae V where R₁, R₂, R₃, and R₄ arealkyl groups, and where R₅ and R₆ are hydrocarbyl, substitutedhydrocarbyl, alkoxy, Cl, Br, and I. Most preferred are1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane-1,2-dimethylhydrazine;[2-(tetramethylphospholyl)ethyl]-[(R,R)-2,7-dimethyl-3,6-decadiyl]phosphine;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methylphenyl)-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-chlorophenyl)-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-tert-butylphenyl)-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-diethynylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(n-propynyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-fluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(phenylethynyl)phosphinoethane;1-(2,3,4,5-tetramethyl-phospholyl)-2-divinylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-dicyclopentylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(n-decyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-fluoro-3-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3,4-difluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-butylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-fluoro-2-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2-naphthyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methyl-thiophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-methoxy-phenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-fluoro-4-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-phenoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-[4-(dimethylamino)phenyl]phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2,4-difluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2,4,6-trimethylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-isopropenylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-diallyl-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-trimethylsilylmethyl-phosphinoethane;and1-(2,3,4,5-tetramethylphospholyl)-2-di-[2-[1,3]dioxan-2-yl-ethyl]phosphinoethane.

Compounds of formula V where X is Cl, Br, or I can be prepared asdetailed above. Other compounds of formula V can be prepared usingcompounds of formula I as an intermediate (Scheme 6).

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, A, and Z are as defined above,

R₉ and R₁₀ are selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl;

M is any metal; and

R₂ and R₃ together and R₅ and R₆ together can optionally form a ring.

An alternative route to compounds of formula V and other compounds isthe synthetic sequence shown in Scheme 7.

Alternate syntheses can be used to prepare bis(phosphole) compounds offormulae II from compounds previously detailed above (Scheme 8).

Another aspect of the present invention provides for novel coordinationcompounds comprising one or more transition metals complexed to one ormore compounds of formulae V or II

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;

R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O and S;

R₂ and R₃ together and R₅ and R₆ together can optionally form a ring;

A is a divalent group consisting of optionally-substituted chains offrom 1 to 12 linear, branched, or cyclic carbons, optionally containingone or more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and

R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

The transition metals are hereby defined as metals of atomic weight 21through 83. Preferred metals are those of Cu(I) or of Periodic GroupVIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt. Mostpreferred is Pd.

Reactions to form coordination compounds use either a well-definedpalladium catalyst such as [(diphosphole)PdMe(CH₃CN)]SbF₆ or catalystsgenerated in situ by mixing the diphospole ligand with palladium saltssuch as [Pd(CH₃CN)₄](BF₄)₂ or Pd(OAc)₂. Catalysts prepared in situ weremade from 1,2-bis(2,3,4,5-tetramethylphospholyl)ethane and Pd(OAc)₂ andfrom 1,3-bis(2,3,4,5-tetraethylphospholyl)propane and [Pd(CH₃CN)₄(BF₄)₂.Preferred coordination compounds are[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMeCl;{[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]-PdMe(CH₃CN)}SbF₆;[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethyl-hydrazine]PdMeCl;and{[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)}SbF₆.

Coordination compounds made in the instant invention can be used ascatalysts for olefin/carbon monoxide polymerizations. The olefin can bean alkene or a cycloalkene containing 2-30, preferably 2-12, carbonatoms. Examples of suitable alkenes can include ethylene, propylene, anyisomeric butene, pentene, hexene, octene, and dodecene, cyclooctene,cyclododecene, styrene, methylstryene, acyrlic acid, methacrylic acid,alkyl esters of acrylic and metacylic acids, and dialkenes in which thetwo unsaturated groups are not conjugated.

Any suitable method to prepare polymer from carbon monoxide and anolefin using the instant catalysts can be used. The catalysts themselvescan be isolated before polymerization or generated in situ. Preferredcatalysts for this process contain Pd.

The ligands made in the instant invention can also be used to prepareCu(I) coordination compounds, which are useful as catalysts in ATRP(atom transfer radical polymerization) processes, as defined above, topolymerize acrylic monomers. The acrylic monomers are of the formula

where R₁ is hydrogen, alkyl, or substituted alkyl group, and R₂ ishydrogen, hydrocarbyl or substituted hydrocarbyl. Preferred arecompounds where R₁ is hydrogen, methyl or ethyl and R₂ is hydrogen ormethyl. Most preferred is where R₁ and R₂ are both methyl(methylmethacrylate).

Any suitable method to prepare the acrylic polymers using the instantcatalysts can be used. The catalysts themselves can be isolated beforepolymerization or generated in situ. Preferred catalysts are thoseformed in situ from 1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane andCuCl.

Materials and Methods

The following non-limiting Examples are meant to illustrate theinvention but are not intended to limit it in any way.

Abbreviations used hereafter are listed and defined below as follows:

DSC Differential scanning calorimetry GPC Gel Permeation chromatographyHFIP 1,1,1,3,3,3-Hexafluoroisopropanol COD 1,5-Cyclooctadiene FID Flameionization detection ATRP Atom transfer radical polymerization MMAMethyl methacrylate ECO Ethylene/carbon monoxide

All manipulations of air-sensitive materials were carried out withrigorous exclusion of oxygen and moisture in flame-dried Schlenk-typeglassware on a dual manifold Schlenk line, interfaced to a high-vacuum(10⁻⁴-10⁻⁵ Torr) line, or in a nitrogen-filled Vacuum Atmospheresglovebox with a high-capacity recirculator (1-2 ppm of O₂). Before use,all solvents were distilled under dry nitrogen over appropriate dryingagents (sodium benzophenone ketyl, metal hydrides except for chlorinatedsolvents). Deuterium oxide and chloroform-d were purchased fromCambridge Isotopes (Andover, Mass.). All organic starting materials werepurchased from Aldrich Chemical Co., Farchan Laboratories Inc. (KennettSquare, Pa.), or Lancaster Synthesis Inc. (Windham, N.H.), and whenappropriate were distilled prior to use. The substrate zirconiummetallacycle (η⁵-C₅H₅)₂ZrC₄Me₄, 2,3,4,5-tetramethylphospholylchloridewere synthesized according to literature procedures. The substrateszirconium metallacycles (η⁵-C₅H₅)₂ZrC₄Et₄,(η⁵-C₅H₅)₂Zr(Me₃C—CCCH₂CH₂CH₂CC—CMe₃), and,2,3,4,5-tetraethylphos-pholylchloride,1,7-ditertbutyl-1,6-bicyclo[3,3]heptadiynyl-phospholylchloride weresynthesized via modifications of literature methods as described below.

Physical and Analytical Measurements

NMR spectra were recorded on either a Nicolet NMC-300 wide-bore (FT, 300MHz, ¹H; 75 MHz, ¹³C, 121 MHz ³¹P), or GE QM-300 narrow-bore (FT, 300MHz, ¹H) instrument. Chemical shifts (δ) for ¹H, ¹³C are referenced tointernal solvent resonances and reported relative to SiMe₄. ³¹P NMRshifts are reported relative to external phosphoric acid. Analytical gaschromatography was performed on a Varian Model 3700 gas chromatographwith FID detectors and a Hewlett-Packard 3390A digitalrecorder/integrator using a 0.125 in i.d. column with 3.8% w/w SE-30liquid phase on Chromosorb W support. GC/MS studies were conducted on aVG 70-250 SE instrument with 70 eV electron impact ionization. Meltingpoints and boiling points are uncorrected.

EXAMPLES

The following Examples are meant to illustrate embodiments of theinvention, but are not intended to limit its scope to the namedelements.

Example 1 Synthesis of 1,2-bis(2,3,4,5-tetramethylphospholyl)ethaneMethod A

A solution of Cp₂ZrC₄Me₄ (2.76 g, 8.47 mmol) in CH₂Cl₂ (60 mL) was addeddropwise to a stirring solution of 1,2-bis(dichlorophosphino)ethane(0.97 g, 4.2 mmol) in CH₂Cl₂ (10 mL) at room temperature over a periodof 10 min, and the resulting reaction mixture was stirred for anadditional 10 min before removal of the solvent under vacuum. Theresidue was extracted with pentane (3×70 mL) and filtered. The filtratewas dried under vacuum, and then sublimated at 130° C./10⁴ Torr toafford 1.0 g (78% yield) of (C₄Me₄P)CH₂CH₂(PC₄Me₄).

¹H NMR (300 MHz, CD₂Cl₂): δ 1.94 (s, 12H, 4Me), 1.91 (s, 12H, 4Me), 1.33(s, 4H, 2CH₂). ¹³C NMR (75 MHz, CD₂Cl₂): δ 143.8 (d, Jp-c=9.8 Hz), 133.2(s), 17.0 (d, Jp-c=23.0 Hz), 14.0 (s), 13.1 (d, Jp-c=21.8 Hz). ³¹P NMR(12 MHz, CD₂Cl₂): δ 16.1 (s). Anal. Calcd for C₁₈H₂₈P₂: C, 70.57; H,9.21; P, 20.22. Found: C, 70.58; H, 9.02; P, 20.23.

Example 2 Method B

A mixture of Cp₂ZrCl₂ (27.0 g, 92.5 mmol) and 2-butyne (16.0 mL, 204mmol) in THF (150 mL) was treated dropwise with n-butyllithium (186mmol, 1.6 M solution in hexane) at −78° C. for 10 min. The resultingreaction suspension was then allowed to stir at room temperature for 2.5hr before cooling to 78° C. 1,2-bis(dichlorophosphino)ethane (10.7 g,46.3 mmol) was added, the mixture was warmed to room temperature andstirred for 30 min before removal of the solvent under vacuum. Theresidue was extracted with pentane (3×100 mL) and filtered. The filtratewas dried under vacuum, and then sublimated at 130° C./10⁴ Torr toafford 9.9 g (70% yield) of (C₄Me₄P)CH₂CH₂(PC₄Me₄).

Example 3 Synthesis of 1,2-bis(2,3,4,5-tetraethylphospholyl)ethane

A procedure similar to that described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method A) above was usedin synthesis of the title compound yielding 5.0 g (92% yield).

¹H NMR (300 MHz, C₆D₆): δ 2.53 (m, 4H), 2.27 (m, 12H), 1.65 (t, J=5.7Hz, 4H), 1.18 (t, J=7.2 Hz, 12H), 0.99 (t, J=7.5 Hz, 12H). ¹³C NMR (75MHz, C₆D₆): δ 148.7, 142.1, 22.0 (d, Jp-c=19.4 Hz), 21.0, 17.8 (d,Jp-c=25.5 Hz), 17.1 (d, Jp-c=8.5 Hz), 15.4. ³¹P NMR (12 MHz, C₆D₆): δ 4(s). MS (rel. abundance): M⁺(33), M⁺−Me(60), M⁺−Et(15), 223.2(6),195.1(26), 167.1(14). High-resolution mass spectrum: Calcd for C₂₆H₄₄P₂(M⁺): 418.2918. Found: 418.2924. Anal. Calcd for C₂₆H₄₄P₂: C, 70.57; H,9.21; P, 20.22. Found: C, 74.14; H, 10.70; P, XX.

Example 4

The procedure was the same as described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method B). The product,(C₄Et₄P)CH₂CH₂(PC₄Et₄), was isolated in 65% yield.

Example 5 Synthesis of1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine

A solution of Cp₂ZrCl₂ (6.67 g, 20.0 mmol) and Cl₂PN(Me)N(Me)PCl₂ (2.3g, 8.6 mmol) in CH₂Cl₂ (150 mL) was refluxed overnight before removal ofthe solvent. The resulting residue was extracted with 3×100 mL ofhexane. After removal of the hexane, the residue was sublimated at 170°C./10⁻⁵ Torr, and then recrystallized from hexane to afford 2.67 g (92%yield) of title compound.

¹H NMR (300 MHz, CD₂Cl₂): δ 2.60 (d, J_(P-H)=3.9 Hz, 6H, 2Me-N), 2.00(d, J_(P-H)=9.9 Hz, 12H, 4Me), 1.84 (d, J_(P-H)=2.7 Hz, 21H, 4Me). ¹³CNMR (75 MHz, CD₂Cl₂): δ 140.2 (d, Jp-c=15.9 Hz), 132.4 (s), 39.4 (s),13.1 (s), 12.8 (d, Jp-c=3.6 Hz). ³¹P NMR (122 MHz, CD₂Cl₂): δ 77.2 (s).MS (rel. abundance): M⁺(61), M⁺−Me(2), 278.1(15), 197.1(31), 168.1(100),139.1 (62). High-resolution mass spectrum: Calcd for C₁₈H₃₀N₂P₂ (M⁺):336.1884. Found: 336.1881.

Example 6 Synthesis of 1,2-bis(2,3,4,5-tetramethylphospholyl)methane

A procedure similar to that described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method A) was used insynthesis of the title compound yielding 1.30 g (97% yield).

¹H NMR (300 MHz, C₆D₆): δ 2.06 (m, 14H), 1.74 (s, 12H). ¹³C NMR (125.7MHz, C₆D₆): δ 142.8, 136.7, 19.3 (t, Jp-c=31.9 Hz), 14.1, 14.0 (t,Jp-c=12.9 Hz). ³¹P NMR (122 MHz, C₆D₆): δ 4.3. MS (rel. abundance):M⁺(96), M⁺+H(100), M⁺−H(30), 153(54). High-resolution mass spectrum:Calcd for C₁₇H₂₆P₂ (M⁺): 292.1510. Found: 292.1513.

Example 7 Synthesis of 11-bis(2,3,4,5-tetraethylphospholyl)methane

A procedure similar to that described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method A) above was usedin synthesis of the title compound (1.70 g, 92% yield).

¹H NMR (300 MHz, C₆D₆): δ 1.02 (t, J=7.6 Hz, 12H), 1.25 (t, J=7.5 Hz,12H), 2.29 (m, 8H), 2.56 (m, 10H). ¹³C NMR (125.7 MHz, C₆D₆): δ 149.0,147.5, 23.8 (t, Jp-c=10.8 Hz), 22.7, 19.5, 17.1. ³¹P NMR (122 MHz,C₆D₆): δ 8.1. MS (rel. abundance): M⁺(33), M³⁰ −H(7), M⁺−Me(7),M⁻-Et(17), 209.1(100), 195.1(22), 181.1(19), 167.198). High-resolutionmass spectrum: Calcd for C₂₅H₄₂P₂ (M⁺): 404.2762. Found: 404.2777.

Example 8 Synthesis of1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophospinoethane

A solution of Cl₂PCH₂CH₂PCl₂ (4.0 g, 16.9 mmol) in CH₂Cl₂ (70 mL) wastreated dropwise with a solution of Cp₂ZrC₄Me₄ (5.6 g, 16.9 mmol) inCH₂Cl₂ (50 mL) at −39° C. over a period of 3 hr. The resulting reactionmixture was then slowly warmed to room temperature and stirred overnightbefore removal of the solvent. The residues were extracted with hexane(3×100 mL) and the extracts were concentrated to give 4.1 g (90% yield)of colorless oil.

¹H NMR (300 MHz, C₆D₆): δ 1.90 (m, 2H), 1.79 (d, J=10.5 Hz, 6H), 1.63(s, 6H), 1.59 (m, 2H). ¹³C NMR (75 MHz, C₆D₆): δ 144.8, 133.0, 37.7 (d,Jp-c=48.8 Hz), 15.2 (dd, J=9.8 Hz), 13.9, 13.0 (d, J=22.0 Hz). ³¹P NMR(122 MHz, C₆D₆): δ 197.7, 11.4. MS (rel. abundance): M⁺(18), 232.0(100),204.0(30), 138.0(82), 123.0(40), 91.1(26). High-resolution massspectrum: Calcd for C₁₀H₁₆Cl₂P₂ (M⁺): 268.0104. Found: 268.0101.

Example 9 Synthesis of1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophospino-1,2-dimethylhydrazine

A procedure analogous to that described above for1-(2,3,4,5-tetra-methylphospholyl)-2-dichlorophospinoethane was used inthe synthesis of this diphosphine derivative with Cp₂ZrC₄Me₄ (6.2 g,18.78 mmol) and Cl₂PN(Me)N(Me)PCl₂ (5.0 g, 18.7 mmol) at roomtemperature. The NMR yield (˜90%) was estimated by the ¹H and ³¹P NMR.

¹H NMR (300 MHz, CD₂Cl₂): δ 3.07 (d, J_(P-H)=5.1 Hz, 3H, Me-NPCl₂), 2.65(dd, J_(P-H)=1.5 Hz, 3H, MeNNPCl₂), 2.00 (d, J_(P-H)=10.5 Hz, 6H, 2Me),1.85 (d, J_(P-H)=3.3 Hz, 6H, 2Me). ¹³C NMR (75 MHz, CD₂Cl₂): δ 143.4 (d,Jp-c=16.9 Hz), 131.2 (s), 39.7 (s), 33.7 (d, Jp-c=6.1 Hz), 13.9 (d,Jp-c=2.4 Hz), 13.0 (d, Jp-c=21.8 Hz). ³¹P NMR (122 MHz, CD₂Cl₂): δ 153.3(d, Jp-p=12.8 Hz), 82.9 (d, Jp-p=14.9 Hz). MS (rel. abundance):M⁺−HCl(24), 227.1(29), 196.0(20), 167.1(90), 137.0(94), 60.0(100),232.0(100), 204.0(30), 138.0(82), 123.0(40), 91.1(26). High-resolutionmass spectrum: Calcd for C₁₀H₁₇N₂P₂Cl (M⁺−HCl): 262.0556. Found:262.0558.

Example 10 Synthesis of 1,3-bis(2,3,4,5-tetraethylphospholyl)propane

Synthesis of (2,3,4,5-tetramethylphospholyl)lithium

To a solution of 1,2-bis(2,3,4,5-tetramethylphospholyl)ethane preparedas described in Example 1, Method A, 5.0 g (16.3 mmol) in THF (70 mL) atroom temperature was added clean Li ribbon (1.0 g, 144.0 mmol) under Ar.The reaction mixture was allowed to stir overnight before filtering outthe excess Li. The filtrate was dried in vacuum to afford 4.7 g (99%yield) of title compound. Reduction of the ethano-bridged diphospholeligand resulted in removal of the bridge (presumably as ethylene) andformation of the tetramethylphospholyl anion. The NMR data agree withliterature data (Douglas et al., 1989, Angew. Chem. Int. Ed. Engl. 28(10), 1367-7.)

Synthesis of (2,3,4,5-tetraethylphospholyl)lithium

A procedure similar to that for (2,3,4,5-tetramethylphospholyl)lithiumdescribed above was used in synthesis of the title compound using1,1-bis(2,3,4,5-tetraethylphospholyl)methane from Example 7 as thestarting material (1.23 g, 98% yield).

¹H NMR (300 MHz, THF-d₈): δ 2.54 (t, J=7.9 Hz, 4H), 2.37 (d, J=7.2 Hz,4H), 1.14 (m, 6H), 0.96 (m, 6H). ³¹P NMR (122 MHz, THF-d₈): δ 56.0.

A suspension of Li C₄Et₄P (1.75 g, 8.67 mmol) in THF (80 mL) was treateddropwise with BrCH₂CH₂CH₂Br (0.88 g, 4.34 mmol) at −30° C. for 10 min.The resulting reaction mixture was then warmed to room temperature andrefluxed overnight. The solution was cooled to room temperature andquenched with CH₃OH (3.0 mL). After removal of the solvents, the residuewas extracted with 3×50 mL of hexane. The combined hexane extracts weredried under reduced pressure to give 0.81 g (44% yield) of(C₄Et₄P)CH₂CH₂CH₂(PC₄Et₄).

¹H NMR (300 MHz, C₆D₆): δ 2.50 (m, 4H), 2.25 (m, 14H), 1.68 (m, 4H), (t,J=7.2 Hz, 12H), 0.99 (t, J=7.2 Hz, 12H). ¹³C NMR (75 MHz, C₆D₆): δ147.9, 142.9, 25.4 (d, Jp-c=17.1 Hz), 22.0 (d, Jp-c=18.3 Hz), 21.5,21.1, 17.4, 15.6. ³¹P NMR (122 MHz, C₆D₆): δ 2.38. MS (rel. abundance):M⁺(17), M⁺−Et(100), 237.2(60). High resolution mass spectrum: Calcd forC₂₇H₄₆P₂ (M⁺): 432.3075. Found: 432.3094.

Examples 11-40 Reaction with Grignards

A set of twenty-eight 5 ml vials were charged with 0.25 mmol each of thefollowing Grignards (Table 1) and 1.0 ml solution of 3 (0.1 mmol) inTHF. The reactions were shaken overnight, and solvent was removed invacuo. Samples were checked by mass spectroscopy (Atmospheric PressureChemical Ionization) for the presence of the expected product. In allcases, the product was observed.

TABLE 1 m/e +1 m/e +1 Example Grignard Concentration Formula expectedfound 11 p-CH₃—C₆H₄MgBr 1.0 M/Ether C₂₄H₃₀P₂ 381.18 381.27 12p-Cl—C₆H₄MgBr 1.0 M/Ether C₂₂H₂₄P₂Cl₂ 421.07 421.19 13p-(CH₃)₃C—C₆H₄MgBr 2.0 M/Ether C₃₀H₄₂P₂ 465.28 465.3 14 H—C≡C—MgBr 0.5M/THF C₁₄H₁₈P₂ 249.08 249.15 15 CH₃C≡CMgBr 0.5 M/THF C₁₆H₂₂P₂ 277.11277.2 16 p-F—C₆H₄MgBr 2.0 M/Ether C₂₂H₂₄P₂F₂ 389.13 389.23 17C₆H₅C≡CMgBr 1.0 M/THF C₂₆H₂₆P₂ 401.15 401.27 18 CH₂═CHMgBr 1.0 M/THFC₁₄H₂₂P₂ 253.12 253.17 19 cyclopentylMgBr 2.0 M/Ether C₂₀H₃₄P₂ 337.21337.31 20 CH₃(CH₂)₉MgBr 1.0 M/Ether C₃₀H₅₈P₂ 481.40 481.57 214-fluoro-3-CH₃—C₆H₃MgBr 1.0 M/THF C₂₄H₂₈P₂F₂ 417.16 417.27 223,4-difluoro-C₆H₃MgBr 0.5 M/THF C₂₂H₂₂P₂F₄ 425.11 425.23 23p-CH₃(CH₂)₃C₆H₄MgBr 0.5 M/THF C₃₀H₄₂P₂ 465.28 465.19 243-fluoro-2-methyl-C₆H₃MgBr 0.5 M/THF C₂₄H₂₈P₂F₂ 417.16 417.28 252-naphthylMgBr 0.25 M/THF C₃₀H₃₀P₂ 453.18 453.31 26 p-CH₃S—C₆H₄MgBr 0.5M/THF C₂₄H₃₀P₂S₂ 445.13 445.25 27 3-methoxy-C₆H₄MgBr 0.5 M/THFC₂₄H₃₀P₂O₂ 413.17 413.34 28 3-fluoro-4-methyl-C₆H₃MgBr 0.5 M/THFC₂₄H₂₈P₂F₂ 417.16 417.3 29 2-methoxy-C₆H₄MgBr 0.5 M/THF C₂₄H₃₀P₂O₂413.17 413.27 30 4-methoxy-C₆H₄MgBr 0.5 M/THF C₂₄H₃₀P₂O₂ 413.17 413.3231 C₆H₅—O—C₆H₄MgBr 0.5 M/THF C₃₄H₃₄P₂O₂ 537.20 537.67 32p-(CH₃)₂NC₆H₄MgBr 0.5 M/THF C₂₆H₃₆P₂N₂ 439.23 439.37 332,4-difluoro-C₆H₃MgBr 0.5 M/THF C₂₂H₂₂P₂F₄ 425.11 425.24 342,4,6-trimethyl-C₆H₂MgBr 1.0 M/THF C₂₈H₃₈P₂ 437.24 437.41 35H₂C═C(CH₃)MgBr 0.5 M/THF C₁₆H₂₆P₂ 281.15 281.21 38 CH₂═CHCH₂MgCl 1.0M/Ether C₁₆H₂₆P₂ 281.15 281.23 39 (CH₃)₃SiCH₂MgCl 1.0 M/EtherC₁₈H₃₈P₂Si₂ 373.20 373.31 40

0.5 M/THF C₂₂H₃₈P₂O₄ 429.22 429.29

Example 41

A flask was charged with 4.00 g (14.9 mmol) of[2-(tetramethyl-phospholyl)ethyl]dichlorophosphine and ca. 30 mL oftetrahydrofuran and was cooled to −30° C. To this was added dropwise 15mL of a 1.0 M solution of lithium aluminum hydride in diethyl ether.After warming to room temperature, tetrahydrofuran was removed in vacuo,and the product was extracted with hexane and filtered. Removal ofhexane in vacuo produced the oily compound[2-(tetra-methylphosphoyl)ethyl]phosphine. ³¹P NMR (122 MHz,tetrahydrofuran-d₈): δ 17 (s), −128 (t, J_((P-H))=190 Hz). This crudeproduct was not purified further. In another flask, 1.30 g of thisproduct (6.49 mmol) was dissolved in 80 mL of tetrahydrofuran, and 5.1mL of 1.6 M n-butyllithium (8.2 mmol) was added to the flask at roomtemperature and this was stirred for one hour. To this was addeddropwise 1.50 g of 2,7-dimethyl-(R,R)-3,6-decadiylsulfate dissolved in 8mL of THF. This was stirred for 1.5 h at room temperature. Then, 5.1 mLof 1.6 M n-butyllithium (8.2 mmol) was added to the flask at roomtemperature and this was stirred for one hour. The reaction mixture wasquenched with 3 mL of methanol, and the solvent was removed in vacuo.The product was extracted with 150 mL of pentane, and was filtered.Removal of pentane in vacuo yielded 1.74 g of[2-(tetramethylphospholyl)ethyl]-[(R,R)-2,7-dimethyl-3,6-decadiyl]phosphinewhich was purified by oil sublimation (160° C., ca. 1 torr). ³¹P{¹H} NMR(122 MHz, C₆D₆): δ 18 (s), −9 (s).

Example 42 Olefin/Carbon Monoxide Copolymerization Using DiphospholeCoordinated Palladium Catalysts Synthesis of[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMeCl

The solution of 1,2-bis(2,3,4,5-tetramethylphospholyl)ethane (1.538 g,5.019 mmol) and (COD)PdMeCl (1.267 g, 4.780 mmol) in 60 mL CH₂Cl₂ wasallowed to stir for 1.5 hr at RT. The mixture was filtered. The filtratewas concentrated to ca. 10 mL, followed by addition of 160 mL pentane.The solid was filtered, washed with 3×10 mL pentane and dried in vacuo.Milky white product (2.128 g, 96%) was obtained. ¹H NMR(CD₂Cl₂): δ0.27(dd, 3H, Pd—CH₃); 1.80-2.14 (m, 28H, overlapped ligand CH₂'s andCH₃'s). ³¹P NMR(CD₂Cl₂): δ 59.63, 73.55 (1P each).

Example 43 Synthesis of{[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMe(CH₃CN)}SbF₆

To a −30° C. solution of[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMeCl (1.47 g, 3.17mmol) and CH₃CN (1.30 g, 31.7 mmol) in 50 mL CH₂Cl₂ was added AgSbF₆(1.090 g, 3.17 mmol). This was allowed to warm up slowly to RT and stirat RT for 30 min. The mixture was filtered. The filtrate wasconcentrated to ca. 5 mL. To the concentrated solution was added 80 mLpentane. The solid was filtered, washed with 3×10 mL pentane and driedin vacuo. Yellow solid (2.172 g, 97%) was obtained. ¹H NMR(CD₂Cl₂): δ0.29(dd, 3H, Pd—CH₃); 1.80-2.20 (m, 28H, overlapped ligand CH₂'s andCH₃'s); 2.24(s, 3H CH₃CN). ³¹P NMR(CD₂Cl₂): δ 60.62, 73.32(d, J=18.0 Hz,1P each).

Example 44 Synthesis of[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl

The solution of1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethyl-hydrazine (0.341 g,1.01 mmol) and (COD)PdMeCl (0.224 g, 0.845 mmol) in 20 mL CH₂Cl₂ wasallowed to stir for 1.5 hr at RT. The mixture was filtered. The filtratewas concentrated to ca. 5 mL, followed by addition of 75 mL pentane. Thesolid was filtered, washed with 3×5 mL pentane and dried in vacuo. Redbrown product (0.253 g, 61%) was obtained. ¹H NMR(CD₂Cl₂): δ 0.25 (dd,3H, Pd—CH₃); 1.98 (s, 12H, 3,4-CH₃'s); 2.01 (dd, 12H, 2,5-CH₃'s); 2.56(d, J=8.4 Hz, 3H, N—CH₃); 2.64 (d, J=10.2 Hz, 3H, N—CH′₃). ³¹PNMR(CD₂Cl₂): δ 115.80 (d, J=30.3 Hz, 1P); 127.40 (d, J=28.9 Hz, 1P).

Example 45 Synthesis of{[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)}SbF₆

To a −30° C. solution of[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl(0.20 g, 0.406 mmol) and CH₃CN (0.17 g, 4.15 mmol) in 20 mL CH₂Cl₂ wasadded AgSbF₆ (0.1394 g, 0.406 mmol). This was allowed to warm up slowlyto RT and stir at RT for 40 min. The mixture was filtered throughCelite® filteration aid. The filtrate was concentrated to ca. 5 mL. Tothe concentrated solution was added 75 mL pentane. The solid wasfiltered, washed with 2×5 mL pentane and dried in vacuo. Light brownsolid (0.23 g, 77%) was obtained. ¹H NMR(CD₂Cl₂): δ 0.27 (dd, 3H,Pd—CH₃); 1.87 (s, 12H, 3,4-CH₃'s); 1.88 (dd, 12H, 2,5-CH₃'s); 2.26 (s,3H CH₃CN); 2.57 (d, J=8.7 Hz, 3H, N—CH₃); 2.67 (d, J=11.1 Hz, 3H,N—CH′₃). ³¹P NMR(CD₂Cl₂): δ 115.58 (d, J=28.5 Hz, 1P); 125.48 (d, J=30.3Hz, 1P).

Polymerizations

Reactions were done by using either well-defined palladium catalystssuch as [(diphosphole)PdMe(CH₃CN)]SbF₆ or catalysts generated in situ bymixing the diphosphole ligand with the palladium salts such as[Pd(CH₃CN)₄](BF₄)₂ or Pd(OAc)₂. Adding strong acid such asp-toluenesulfonic acid is important when Pd(OAc)₂ is used as thecatalyst precursor. Adding excess of benzoquinone as the oxidant ingeneral helps the copolymer yield. The copolymerization works in commonorganic solvents such as CH₂Cl₂, chlorobenzene and methanol. Thesynthesis of the organometallic complexes were carried out in a nitrogendrybox. Catalyst screening was more conveniently done in multishakertubes. When using shaker tubes for ligand and catalyst scouting (Table2), 25 mL-sized tubes were used. Ligand, catalyst precursor (orsingle-component catalyst), oxidant (sometimes also p-CH₃C₆H₄SO₃.H₂Oacid) and 5 mL of specified solvent(s) were mixed in the shaker tubes.After purging with nitrogen, these tubes were pressured up withethylene/CO (1:1) mixed gas and was shaken at 60° C. under ethylene/COpressure for 18 hr.

Example 46 High Pressure Slurry ECO Copolymerization (100° C. 900 psi)

{[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMe(CH₃CN)}SbF₆ (1.00 g,1.42 mmole), benzoquinone (3.07 g, 28.4 mmole) and 1460 mL methanol werecharged into an one gallon autoclave. The reactor was then charged withmixed ethylene/carbon monoxide gas (1:1) and the temperature was raisedup to 100° C. The mixture was allowed to stir at 100° C. under 900 psiof E/CO mixed gas for 6 hr. The reaction was exothermic(cooling coil wasused to control the temperature by using water as coolant). Uponcooling, the polymer/methanol mixture was transferred to a blender andwas blended to powders. The powdery polymer was then filtered, washedwith methanol repeatedly and dried in vacuo at 100° C. for 3 days. Whitepowdery polymer (356 g) was obtained. Based on ¹H and ¹³C NMR, thepolymer is perfectly alternating ethylene/CO copolymer. The copolymerexhibited a m.p. of 250° C. based on DSC. GPC (HFIP, polyethyleneterephthalate standard): Mw=236,000; Mn=46,800; Mw/Mn=5.0.

Example 47 Slurry ECO Copolymerization (60° C., 700 psi)

{[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMe(CH₃CN)}SbF₆ (0.60 g,0.852 mmole), benzoquinone (4.6 g, 42.6 mmole), 1000 mL methanol and 500mL toluene were charged into an one gallon autoclave. The reactor wasthen charged with mixed ethylene/carbon monoxide gas (1:1) and thetemperature was raised up to 60° C. The mixture was allowed to stir at60° C. under 700 psi of ECO mixed gas for 6 hr. The reaction wasexothermic (cooling coil was used to control the temperature by usingwater as coolant). Upon cooling, the polymer/methanol mixture wastransferred to a blender and was blended to powders. The powdery polymerwas then filtered, washed with methanol repeatedly and dried in vacuo at100° C. for one day. White powdery polymer (243 g) was obtained. Basedon ¹H and ¹³C NMR, the polymer is perfectly alternating ethylene/COcopolymer. The copolymer exhibited a m.p. of 242° C. based on DSC. GPC(HFIP, polyethylene terephthalate standard): Mw=149,000; Mn=63,000;Mw/Mn=2.4.

Examples 48-53 Shaker Tube Screening of Ligands and Catalysts for ECOCopolymerization (60° C., 18 hr)

TABLE 1 Shaker tube experiments for Ethylene/CO copolymerizationCatalyst or E/CO Ligand precursor Benzoquinone Acid Pressure Copolymerm.p Ex. (mg) (mg) (mg) (mg) Solvent (psi) Mw/Mn Yield (g) (° C.) 48 0C-1 (4.7) 14.4 0 CH₃OH 708 na 8.5 na 49 0 C-1 (42) 0 0 CH₃OH 880 na 23.3na 50 L-1 Pd(OAc)₂ 130 228 CH₃OH/ 800 na 0.5 na (22) (12.5) toluene 2:151 0 C-1 (2.0) 6.3 0 CH₃OH 885 381,000/ 1.53 253 151,000 52 0 C-2 (29.4)89.6 0 CH₃OH 885 509,000/ 5.0 245 218,000 53 L-2 P-1 (5.7) 27.6 0 CH₃OH600 707,000/ 11.8 na (5.5) 312,000 L-1 =1,2-bis(2,3,4,5-tetramethylphospholyl)ethane L-2 =1,3-bis(2,3,4,5-tetraethylphospholyl)propane C-1 ={[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMe(CH₃CN)}SbF₆ C-2 ={[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)}SbF₆P-1 = [Pd(CH₃CN)₄](BF₄)₂

Example 54 ATRP of MMA Using Cu(I)-diphosphole Complex as Catalyst

MMA was passed through a basic alumina column to remove inhibitor, thendegassed by freeze-thaw cycle three times. 10 mg of CuCl and 62 mg of1,2-bis(2,3,4,5-tetramethylphospholyl) ethane were put into 5.0 mL ofdegassed toluene. 5.0 mL of purified MMA and 66 μL of2,2′-dichloroacetophenone were added into the above catalyst solution.The solution was mixed well in a Schlenck flask and the flask was sealedunder nitrogen and then immersed in an oil bath set at 80° C.Polymerization proceeded at 80° C. with stirring for 16 hrs. Afterpolymerization was stopped, the solution was diluted with more tolueneand then polymer was precipitated into methanol. Polymer solid wascollected by filtration, washed with methanol, and dried under vacuum.0.35 g polymer was obtained (7.5% conversion of MMA). The polymer wasanalyzed by GPC with THF as eluent and PMMA as standard. The numberaverage molecular weight (M_(n)) was 20200 and M_(w)/M_(n) was 1.32.

1. A process for polymerizing an acrylic monomer comprising contactingat least one acrylic monomer under polymerization conditions with acatalyst comprising Cu(I) complexed with one or more ligands comprisingphosphorus containing rings of the formulae V or II

wherein the phosphorus containing rings are optionally-substituted andare optionally members of a larger bicyclic or tricyclic ring system;each P atom is bonded to only three other atoms in the ligand; the twoatoms in the ring adjacent to the P atom are C atoms; R₁, R₂, R₃, and R₄are independently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl; R₅ and R₆ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, substitutedhydrocarbyl, Cl, Br, I, hydroxyl, alkoxy, thiol, alkylthio, amino,alkylamino, and dialkylamino; R₂ and R₃ together and R₅ and R₆ togethercan optionally form a ring; A is a divalent group ofoptionally-substituted chains of from 1 to 12 linear, branched, orcyclic carbons, optionally containing one or more heteroatoms ororganometallic groups in the chain, and —N(R₇)—N(R₈)—; and R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.
 2. The process of claim 1wherein the ligand is of the formulae V or II

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.
 3. Theprocess of claim 1 wherein A is selected from the group consisting of acarbon chain of 1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.
 4. The process of claim 3wherein R₁, R₂, R₃, and R₄ are alkyl groups.
 5. The complex of claim 4wherein R₅ and R₆ are selected from the group consisting of alkyl groupsand Cl.
 6. The process of claim 1 wherein the acrylic monomer ismethyl-methacrylate.
 7. The process of claim 1 wherein the catalyst ispreapred in situ from 1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane andCuCl.